New synthetic routes to cationic rhenium tricarbonyl bipyridine complexes with labile ligands

E Hevia, J Perez, V Riera, D Miguel, S Kassel, A Rheingold

Research output: Contribution to journalArticle

45 Citations (Scopus)

Abstract

Triflate abstraction from the complex [Re(OTf)(CO)(3)(bipy)] (1) using the salt NaBAr'(4) (Ar' = 3,5-bis(trifluoromethyl)phenyl) in dichloromethane solution in the presence of L = PPh3, NCMe, NCPh, imines, ketones, Et2O, THF, MeOH, and Mel affords cationic complexes [Re(L)(CO)(3)(bipy)](+) as their BAr'(-)(4) salts. The new complexes have been characterized spectroscopically and, for [Re(eta1-O=C(Me)R)(CO)(3)(bipy)]BAr'(4) (R = CH3, 6a; R = Ph, 6b), and [Re(THF)(CO)(3)(bipy)]BAr'(4) (9), also by single-crystal X-ray diffraction. Compared with conventional methodologies, the route reported here allows the coordination of a broader range of weakly coordinating ligands and requires considerably milder conditions. On the other hand, the reactions of lithium acetylides with [Re(THF)(CO)(3)(bipy)]BAr'(4) (9) can be used for the high-yield syntheses of rhenium alkynyls [Re(Cequivalent toCR)(CO)(3)(bipy)] (R = Ph, 12; R SiMe3, 13). Complex 9 was found to catalyze the aziridination of benzylideneaniline with ethyl diazoacetate.

LanguageEnglish
Pages4673-4679
Number of pages7
JournalInorganic Chemistry
Volume41
Issue number18
DOIs
Publication statusPublished - 9 Sep 2002

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Rhenium
rhenium
Carbon Monoxide
routes
Ligands
salts
ligands
ketones
imines
lithium
methodology
single crystals
synthesis
Salts
diffraction
x rays
Imines
Methylene Chloride
Ketones
Lithium

Keywords

  • carbonyl-diimine complexes
  • organometallic chemistry
  • co2 reduction
  • Lewis acid
  • reactivity
  • binding
  • luminescent
  • alkoxides

Cite this

Hevia, E ; Perez, J ; Riera, V ; Miguel, D ; Kassel, S ; Rheingold, A . / New synthetic routes to cationic rhenium tricarbonyl bipyridine complexes with labile ligands. In: Inorganic Chemistry. 2002 ; Vol. 41, No. 18. pp. 4673-4679.
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abstract = "Triflate abstraction from the complex [Re(OTf)(CO)(3)(bipy)] (1) using the salt NaBAr'(4) (Ar' = 3,5-bis(trifluoromethyl)phenyl) in dichloromethane solution in the presence of L = PPh3, NCMe, NCPh, imines, ketones, Et2O, THF, MeOH, and Mel affords cationic complexes [Re(L)(CO)(3)(bipy)](+) as their BAr'(-)(4) salts. The new complexes have been characterized spectroscopically and, for [Re(eta1-O=C(Me)R)(CO)(3)(bipy)]BAr'(4) (R = CH3, 6a; R = Ph, 6b), and [Re(THF)(CO)(3)(bipy)]BAr'(4) (9), also by single-crystal X-ray diffraction. Compared with conventional methodologies, the route reported here allows the coordination of a broader range of weakly coordinating ligands and requires considerably milder conditions. On the other hand, the reactions of lithium acetylides with [Re(THF)(CO)(3)(bipy)]BAr'(4) (9) can be used for the high-yield syntheses of rhenium alkynyls [Re(Cequivalent toCR)(CO)(3)(bipy)] (R = Ph, 12; R SiMe3, 13). Complex 9 was found to catalyze the aziridination of benzylideneaniline with ethyl diazoacetate.",
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author = "E Hevia and J Perez and V Riera and D Miguel and S Kassel and A Rheingold",
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New synthetic routes to cationic rhenium tricarbonyl bipyridine complexes with labile ligands. / Hevia, E ; Perez, J ; Riera, V ; Miguel, D ; Kassel, S ; Rheingold, A .

In: Inorganic Chemistry, Vol. 41, No. 18, 09.09.2002, p. 4673-4679.

Research output: Contribution to journalArticle

TY - JOUR

T1 - New synthetic routes to cationic rhenium tricarbonyl bipyridine complexes with labile ligands

AU - Hevia, E

AU - Perez, J

AU - Riera, V

AU - Miguel, D

AU - Kassel, S

AU - Rheingold, A

PY - 2002/9/9

Y1 - 2002/9/9

N2 - Triflate abstraction from the complex [Re(OTf)(CO)(3)(bipy)] (1) using the salt NaBAr'(4) (Ar' = 3,5-bis(trifluoromethyl)phenyl) in dichloromethane solution in the presence of L = PPh3, NCMe, NCPh, imines, ketones, Et2O, THF, MeOH, and Mel affords cationic complexes [Re(L)(CO)(3)(bipy)](+) as their BAr'(-)(4) salts. The new complexes have been characterized spectroscopically and, for [Re(eta1-O=C(Me)R)(CO)(3)(bipy)]BAr'(4) (R = CH3, 6a; R = Ph, 6b), and [Re(THF)(CO)(3)(bipy)]BAr'(4) (9), also by single-crystal X-ray diffraction. Compared with conventional methodologies, the route reported here allows the coordination of a broader range of weakly coordinating ligands and requires considerably milder conditions. On the other hand, the reactions of lithium acetylides with [Re(THF)(CO)(3)(bipy)]BAr'(4) (9) can be used for the high-yield syntheses of rhenium alkynyls [Re(Cequivalent toCR)(CO)(3)(bipy)] (R = Ph, 12; R SiMe3, 13). Complex 9 was found to catalyze the aziridination of benzylideneaniline with ethyl diazoacetate.

AB - Triflate abstraction from the complex [Re(OTf)(CO)(3)(bipy)] (1) using the salt NaBAr'(4) (Ar' = 3,5-bis(trifluoromethyl)phenyl) in dichloromethane solution in the presence of L = PPh3, NCMe, NCPh, imines, ketones, Et2O, THF, MeOH, and Mel affords cationic complexes [Re(L)(CO)(3)(bipy)](+) as their BAr'(-)(4) salts. The new complexes have been characterized spectroscopically and, for [Re(eta1-O=C(Me)R)(CO)(3)(bipy)]BAr'(4) (R = CH3, 6a; R = Ph, 6b), and [Re(THF)(CO)(3)(bipy)]BAr'(4) (9), also by single-crystal X-ray diffraction. Compared with conventional methodologies, the route reported here allows the coordination of a broader range of weakly coordinating ligands and requires considerably milder conditions. On the other hand, the reactions of lithium acetylides with [Re(THF)(CO)(3)(bipy)]BAr'(4) (9) can be used for the high-yield syntheses of rhenium alkynyls [Re(Cequivalent toCR)(CO)(3)(bipy)] (R = Ph, 12; R SiMe3, 13). Complex 9 was found to catalyze the aziridination of benzylideneaniline with ethyl diazoacetate.

KW - carbonyl-diimine complexes

KW - organometallic chemistry

KW - co2 reduction

KW - Lewis acid

KW - reactivity

KW - binding

KW - luminescent

KW - alkoxides

U2 - 10.1021/ic020174c

DO - 10.1021/ic020174c

M3 - Article

VL - 41

SP - 4673

EP - 4679

JO - Inorganic Chemistry

T2 - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 18

ER -